JPH10265791A - Low-ash lubricant containing ultra-neutral zinc dialkyldithiophosphate - Google Patents

Low-ash lubricant containing ultra-neutral zinc dialkyldithiophosphate

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Publication number
JPH10265791A
JPH10265791A JP10072383A JP7238398A JPH10265791A JP H10265791 A JPH10265791 A JP H10265791A JP 10072383 A JP10072383 A JP 10072383A JP 7238398 A JP7238398 A JP 7238398A JP H10265791 A JPH10265791 A JP H10265791A
Authority
JP
Japan
Prior art keywords
weight
lubricating oil
zinc
oil composition
zinc dialkyldithiophosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10072383A
Other languages
Japanese (ja)
Inventor
S Yamaguchi Elaine
エス．ヤマグチ イレーヌ
R Ruue William Jr
アール．ルーエ ジュニア． ウィリアム
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Phillips Chemical Co LP
Original Assignee
Chevron Chemical Co LLC
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Filing date
Publication date
Application filed by Chevron Chemical Co LLC filed Critical Chevron Chemical Co LLC
Publication of JPH10265791A publication Critical patent/JPH10265791A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
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    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/251—Alcohol fueled engines
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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Biochemistry (AREA)
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  • Lubricants (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a low-ash lubricant excellent in abrasion-preventing activity by compounding an ultra-neutral zinc dialkyldithiophosphate as an abrasion- preventing agent. SOLUTION: This low-ash lubricant is composed of (A) a base oil having a lubrication viscosity and (B) an ultra-neutral zinc dialkyldithiophosphate having a zinc vs. phosphorus weight ratio in the range of (0.95:1) to (1.04:1), and its ash content is less than 1.5 wt.% (preferably, less than 1.0 wt.%). The component B is compounded at a ratio of 0.O5-5 wt.%, preferably 0.05-3 wt.% based on the total weight of an engine oil. Besides the components A and B, optionally an ash-free dispersing agent, a perbasic alkyl phenate sulfide dispersing agent, an antioxidant, a viscosity index improving agent, etc., is added.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、摩耗防止剤として
の超中性(ultra-neutral）ジアルキルジチオ燐酸亜鉛を
含む低灰分潤滑油に関する。The present invention relates to low ash lubricating oils containing ultra-neutral zinc dialkyldithiophosphates as antiwear agents.

【０００２】[0002]

【従来の技術】或る油特性を改良し、一層満足できる潤
滑油を製造するために、種々の添加剤を潤滑油に用いる
ことができることはよく知られている。例えば、摩耗防
止剤は機械部品の摩耗を減少する。高性能エンジン中の
運動する部品の摩耗を防ぐため、モーターオイル及び工
業的油の中に摩耗防止剤を配合する。そのような油組成
物には、その潤滑特性を改良し、運動部品の摩耗を減少
させるため、数多くの他の添加剤が開発されてきた。It is well known that various additives can be used in lubricating oils to improve certain oil properties and produce more satisfactory lubricating oils. For example, antiwear agents reduce the wear of machine parts. Anti-wear agents are incorporated into motor oils and industrial oils to prevent wear of moving parts in high performance engines. Numerous other additives have been developed in such oil compositions to improve their lubricating properties and reduce wear of moving parts.

【０００３】摩耗防止剤の中で、ジアルキルジチオ燐酸
亜鉛（ＺｎＤＴＰ）は、作動油、モーターオイル、自動
変速機油等の摩耗防止添加剤及び酸化防止剤として長い
間用いられてきた。ジアルキルジチオ燐酸亜鉛の製造方
法はよく知られている。米国特許第２，８３８，５５５
号、第３，８４８，０３２号、第４，０８５，０５３
号、第４，１２３，３７０号、第４，２１５，０６７
号、及び第４，２６３，１５０号明細書（それらは全て
の目的に対し、引用して全て本願明細書に組込んであ
る）参照。典型的な反応として、４当量のヒドロキシア
ルキル化合物を、五硫化燐と反応させる。ジアルキルジ
チオ燐酸が形成されたならば、次にそれを過剰の酸化亜
鉛で中和する。[0003] Among antiwear agents, zinc dialkyldithiophosphates (ZnDTP) have long been used as antiwear additives and antioxidants in hydraulic oils, motor oils, automatic transmission oils and the like. Methods for producing zinc dialkyldithiophosphate are well known. U.S. Pat. No. 2,838,555
No. 3,848,032, 4,085,053
No. 4,123,370, 4,215,067
And U.S. Pat. No. 4,263,150, which are incorporated herein by reference for all purposes. As a typical reaction, 4 equivalents of a hydroxyalkyl compound are reacted with phosphorus pentasulfide. Once the dialkyldithiophosphoric acid has formed, it is then neutralized with excess zinc oxide.

【０００４】ジアルキルジチオ燐酸亜鉛の摩耗防止性を
決定する時の重要な特性は、亜鉛対燐比である。亜鉛対
燐比は、約１．１５：１以上であるべきであり、好まし
くは約１．２０：１より大きいのが良いと言うのが典型
的な従来の考え方であった。An important property in determining the antiwear properties of zinc dialkyldithiophosphates is the zinc to phosphorus ratio. It was a typical conventional belief that the zinc to phosphorus ratio should be greater than or equal to about 1.15: 1, and preferably greater than about 1.20: 1.

【０００５】米国特許第３，６９１，２２０号明細書 この特許は、過塩基性ジチオ燐酸亜鉛の製造方法を教示
している。これは、「中性」ジチオ燐酸亜鉛が１．０
６：１の亜鉛対燐比を有することを述べている。US Pat. No. 3,691,220 This patent teaches a method for making overbased zinc dithiophosphate. This is because "neutral" zinc dithiophosphate is 1.0%.
It has a zinc to phosphorus ratio of 6: 1.

【０００６】米国特許第４，０９４，８００号明細書 この特許は、基礎油、アルコール又はアミン、及び１．
１５：１〜１．５：１の亜鉛対燐重量比、好ましくは
１．１５：１〜１．３５：１の亜鉛対燐重量比を有する
第一級ジアルキルジチオ燐酸亜鉛を含む潤滑油組成物を
教示している。US Pat. No. 4,094,800 This patent discloses base oils, alcohols or amines, and 1.
Lubricating oil composition comprising a zinc primary dialkyldithiophosphate having a zinc to phosphorus weight ratio of 15: 1 to 1.5: 1, preferably a zinc to phosphorus weight ratio of 1.15: 1 to 1.35: 1. Is taught.

【０００７】米国特許第４，５９２，８５１号明細書 この特許は、基礎油、及び１．１５：１〜１．６５：１
の亜鉛対燐重量比、好ましくは１．２０：１〜１．５：
１の亜鉛対燐重量比を有する第一級ジアルキルジチオ燐
酸亜鉛を含む潤滑油組成物を教示している。US Pat. No. 4,592,851 This patent discloses a base oil and 1.15: 1 to 1.65: 1.
Weight ratio of zinc to phosphorus, preferably 1.20: 1 to 1.5:
It teaches a lubricating oil composition comprising a zinc primary dialkyldithiophosphate having a zinc to phosphorus weight ratio of one.

【０００８】米国特許第５，３２６，４８５号明細書 この特許は、酸化防止剤、過塩基性アルカリ土類金属硫
化アルキルフェネート、及び第一級ジアルキルジチオ燐
酸亜鉛を含有する低灰分潤滑油組成物を教示している。
ジアルキルジチオ燐酸亜鉛の塩基対中性塩比は、31Ｐ核
磁気共鳴（ＮＭＲ）分光分析により少なくとも０．９６
である。US Pat. No. 5,326,485 This patent discloses a low ash lubricating oil composition containing an antioxidant, an overbased alkaline earth metal sulfurized alkyl phenate, and a zinc primary dialkyldithiophosphate. Teaching things.
The base to neutral salt ratio of the zinc dialkyldithiophosphate should be at least 0.96 by 31 P nuclear magnetic resonance (NMR) spectroscopy.
It is.

【０００９】米国特許第５，３８０，４４８号明細書 この特許は、１．２：１〜１．３：１の亜鉛対燐重量比
を有する過塩基性ジアルキルジチオ燐酸亜鉛塩の製造方
法を教示している。US Pat. No. 5,380,448 This patent teaches a process for preparing an overbased zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio of 1.2: 1 to 1.3: 1. doing.

【００１０】米国特許第５，３８４，０５４号明細書 この特許は、１．１５：１〜１．３：１の亜鉛対燐重量
比を有する過塩基性ジアルキルジチオ燐酸亜鉛塩を製造
する方法を教示している。US Pat. No. 5,384,054 This patent describes a process for preparing an overbased zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio of 1.15: 1 to 1.3: 1. Teaching.

【００１１】[0011]

【発明が解決しようとする課題】本発明は、優れた摩耗
防止性能を有する低灰分潤滑油組成物を与える。SUMMARY OF THE INVENTION The present invention provides a low ash lubricating oil composition having excellent antiwear properties.

【００１２】[0012]

【課題を解決するための手段】本発明の低灰分潤滑油組
成物は、潤滑粘度の基礎油及び超中性ジアルキルジチオ
燐酸亜鉛を含有する。SUMMARY OF THE INVENTION The low ash lubricating oil composition of the present invention comprises a base oil of lubricating viscosity and a super-neutral zinc dialkyldithiophosphate.

【００１３】本発明は、ジアルキルジチオ燐酸亜鉛の分
野での基本的研究から生まれたものである。ジアルキル
ジチオ燐酸塩の超中性亜鉛塩が、ジアルキルジチオ燐酸
塩の塩基性亜鉛塩よりも一層よい摩耗防止性能を与える
と言うことが発見された。これは全く意外なことであ
る。なぜなら、常に塩基性ジアルキルジチオ燐酸亜鉛塩
が一層よい性能を与えると言うことが従来の考え方であ
ったからである。The present invention has resulted from basic research in the field of zinc dialkyldithiophosphates. It has been discovered that super-neutral zinc salts of dialkyl dithiophosphates provide better antiwear performance than basic zinc salts of dialkyl dithiophosphates. This is completely surprising. This is because it has been a conventional idea that a basic zinc salt of dialkyldithiophosphate always gives better performance.

【００１４】この改良を生ずる機構については不確かで
あるが、超中性ジアルキルジチオ燐酸亜鉛塩が溶液中オ
リゴマーとして存在する傾向があり、一方塩基性塩は単
一の分子として存在する傾向があると我々は考えてい
る。溶液中、超中性塩は、１単位当たり一層多くの極性
官能基が存在するため、表面に吸着される一層大きな傾
向を有する。この吸着段階がないと、摩耗防止は行うこ
とができない。大きなオリゴマーは金属表面に優先的に
吸着される傾向があり、これによって摩耗防止性を与え
る。これらの大きなオリゴマーが吸着されると、溶液の
平衡は、一層多くのこれら大きなオリゴマーを与える方
向に移動して再び平衡になる。塩基性塩と金属表面との
相互作用は順調には進行しない。この現象は従来の研究
では見られていない。なぜなら、殆どの摩耗防止ベンチ
テストは、吸着効果を示していないからである。Although the mechanism that causes this improvement is uncertain, it is believed that super-neutral zinc dialkyldithiophosphates tend to exist as oligomers in solution, while basic salts tend to exist as single molecules. We are thinking. In solution, super-neutral salts have a greater tendency to be adsorbed on the surface due to the presence of more polar functional groups per unit. Without this adsorption step, wear protection cannot be achieved. Larger oligomers tend to preferentially adsorb to metal surfaces, thereby providing antiwear properties. As these large oligomers are adsorbed, the equilibrium of the solution will move in a direction that gives more of these large oligomers and re-equilibrate. The interaction between the basic salt and the metal surface does not proceed smoothly. This phenomenon has not been seen in previous studies. This is because most anti-wear bench tests show no adsorption effect.

【００１５】「超中性ジアルキルジチオ燐酸亜鉛」と
は、０．９５：１〜１．０４：１の範囲の亜鉛対燐重量
比を有するジアルキルジチオ燐酸亜鉛を意味する。超中
性ジアルキルジチオ燐酸亜鉛は、それらが一層低い亜鉛
対燐比を有すると言う点で「中性」ジアルキルジチオ燐
酸亜鉛とは区別されるものである。従来の考え方は、常
に「中性」ジアルキルジチオ燐酸亜鉛が１．０５：１又
は１．０６：１の亜鉛対燐比を有すると言うことにあっ
た。By "super-neutral zinc dialkyldithiophosphate" is meant zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio in the range of 0.95: 1 to 1.04: 1. Superneutral zinc dialkyldithiophosphates are distinguished from "neutral" zinc dialkyldithiophosphates in that they have a lower zinc to phosphorus ratio. The conventional idea was to always say that "neutral" zinc dialkyldithiophosphates had a zinc to phosphorus ratio of 1.05: 1 or 1.06: 1.

【００１６】中性又は塩基性ジアルキルジチオ燐酸亜鉛
の量を分析するために、慣用的31ＰＮＭＲ法を用いた。
これらの方法によれば、第一級ジアルキルジチオ燐酸亜
鉛からの塩基性物質は、スペクトル中約１０３〜１０５
ｐｐｍの範囲内に現れるが、第二級ジアルキルジチオ燐
酸亜鉛から誘導されたものは、スペクトル中約９８〜１
００ｐｐｍの範囲に現れる。一方、第一級ジアルキルジ
チオ燐酸亜鉛からの中性物質は、スペクトル中約１００
〜１０２ｐｐｍの範囲に現れるのに対し、第二級ジアル
キルジチオ燐酸亜鉛から誘導されたものは、約９２〜９
４ｐｐｍの範囲に現れる。これらの信号を通常のやり方
で積分して相対的量を計算する。A conventional 31 P NMR method was used to analyze the amount of neutral or basic zinc dialkyldithiophosphate.
According to these methods, the basic substance from the primary zinc dialkyldithiophosphate is approximately 103-105 in the spectrum.
Although appearing in the ppm range, those derived from secondary zinc zinc dialkyldithiophosphates have about 98-1
Appears in the range of 00 ppm. On the other hand, neutral substances from primary zinc dialkyldithiophosphate show about 100% in the spectrum.
Those derived from secondary zinc dialkyldithiophosphates appear in the range of about 92-9
Appears in the 4 ppm range. These signals are integrated in the usual manner to calculate the relative quantities.

【００１７】従来の文献は、中性ジアルキルジチオ燐酸
亜鉛塩は１．０５：１の亜鉛対燐重量比を有することを
教示している。なぜなら、ジアルキルジチオ燐酸亜鉛が
次の構造（Ｒ及びＲ′はアルキル基である）、Prior literature teaches that neutral zinc dialkyldithiophosphates have a zinc to phosphorus weight ratio of 1.05: 1. Because zinc dialkyldithiophosphate has the following structure (R and R 'are alkyl groups):

【００１８】[0018]

【化１】 Embedded image

【００１９】を有するものと仮定していたからである。This is because it is assumed to have

【００２０】１．０５の亜鉛対燐重量比を有するジアル
キルジチオ燐酸亜鉛塩は、31Ｐ ＮＭＲ分光分析により
決定して、約１０重量％の塩基性塩を含むことが見出さ
れた。一層低い亜鉛対燐重量比を有するジアルキルジチ
オ燐酸亜鉛塩は、他の性質に有害な影響を与えることな
く、一層よい摩耗防止性を与えると言うことも見出され
た。The zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio of 1.05 was found to contain about 10% by weight of the basic salt as determined by 31 P NMR spectroscopy. It has also been found that zinc dialkyldithiophosphates having lower zinc to phosphorus weight ratios provide better antiwear properties without adversely affecting other properties.

【００２１】潤滑油の灰分含有量はかなり変化するが、
本願の目的にとっては、用語「低灰分」とは、１．５重
量％より少ない灰分含有量を意味する。好ましくは潤滑
油組成物の灰分含有量は１．１重量％より少なく、一層
好ましくは１．０重量％より少ない。潤滑油組成物の灰
分含有量は、ジアルキルジチオ燐酸亜鉛の摩耗防止性の
劣化を防ぐために低くあるべきである。The ash content of the lubricating oil varies considerably,
For the purposes of the present application, the term “low ash” means an ash content of less than 1.5% by weight. Preferably, the ash content of the lubricating oil composition is less than 1.1% by weight, more preferably less than 1.0% by weight. The ash content of the lubricating oil composition should be low to prevent degradation of the anti-wear properties of the zinc dialkyldithiophosphate.

【００２２】ジアルキルジチオ燐酸亜鉛のアルキル基の
各々は、３〜２０個の炭素原子を有するのが好ましい。
一層好ましくは、アルキル基の各々は３〜８個の炭素原
子を有する。ジアルキルジチオ燐酸亜鉛のアルキル基の
各々は第二級アルキル基であるのが好ましい。Each of the alkyl groups of the zinc dialkyldithiophosphate preferably has from 3 to 20 carbon atoms.
More preferably, each of the alkyl groups has 3 to 8 carbon atoms. Each of the alkyl groups of the zinc dialkyldithiophosphate is preferably a secondary alkyl group.

【００２３】一つの態様として、低灰分潤滑油組成物
は、潤滑油粘度の基礎油、無灰分散剤、過塩基性硫化ア
ルキルフェネート分散剤、酸化防止剤、粘度指数改良剤
及び超中性ジアルキルジチオ燐酸亜鉛を含有する。In one embodiment, the low ash lubricating oil composition comprises a base oil of lubricating oil viscosity, an ashless dispersant, an overbased sulfurized alkyl phenate dispersant, an antioxidant, a viscosity index improver and a super neutral dialkyl. Contains zinc dithiophosphate.

【００２４】[0024]

【発明の実施の形態】最も広い態様として、本発明は、
優れた摩耗防止性能を有する低灰分潤滑油組成物を包含
する。その低灰分潤滑油組成物は、潤滑油粘度の基礎油
及び超中性ジアルキルジチオ燐酸亜鉛を含有する。超中
性ジアルキルジチオ燐酸亜鉛は、一般にエンジンオイル
の全量当たり０．０５〜５重量％、好ましくは０．０５
〜３重量％の量でエンジン油に配合される。DETAILED DESCRIPTION OF THE INVENTION In its broadest aspect, the present invention provides:
Low ash lubricating oil compositions having excellent antiwear performance. The low ash lubricating oil composition contains a base oil of lubricating oil viscosity and a super neutral zinc dialkyldithiophosphate. The super-neutral zinc dialkyldithiophosphate is generally present in an amount of 0.05 to 5% by weight, preferably 0.05% by weight, based on the total weight of the engine oil.
It is incorporated into engine oils in amounts of up to 3% by weight.

【００２５】超中性ジアルキルジチオ燐酸亜鉛は、式：The super-neutral zinc dialkyldithiophosphate has the formula:

【００２６】[0026]

【化２】 Embedded image

【００２７】のジアルキルジチオ燐酸から製造すること
ができる。From the dialkyldithiophosphoric acid.

【００２８】ジアルキルジチオ燐酸を誘導することがで
きるヒドロキシアルキル化合物は、一般に式ＲＯＨ又は
Ｒ′ＯＨ（式中、Ｒ又はＲ′はアルキル又は置換アルキ
ル基である）により表すことができる。Ｒ又はＲ′は、
好ましくは、３〜２０個の炭素原子を有する分岐又は非
分岐又は環式アルキルであり、一層好ましくは３〜８個
の炭素原子を有する分岐又は非分岐又は環式第二級アル
キルであり、最も好ましくは、アルキル基が１分子当た
り平均約４．５の炭素を有する第二級アルコール混合物
から誘導されたジアルキルジチオ燐酸である。Hydroxyalkyl compounds from which dialkyldithiophosphoric acids can be derived can generally be represented by the formula ROH or R'OH, where R or R 'is an alkyl or substituted alkyl group. R or R 'is
Preferably, it is a branched or unbranched or cyclic alkyl having 3 to 20 carbon atoms, more preferably a branched or unbranched or cyclic secondary alkyl having 3 to 8 carbon atoms, most preferably Preferred are dialkyldithiophosphoric acids in which the alkyl groups are derived from a mixture of secondary alcohols having an average of about 4.5 carbons per molecule.

【００２９】ヒドロキシアルキル化合物の混合物も用い
ることができる。当分野で認識されているように、これ
らのヒドロキシアルキル化合物はモノヒドロキシアルキ
ル化合物である必要はない。即ち、ジアルキルジチオ燐
酸は、モノ−、ジ−、トリ−、テトラ−、及び他のポリ
−ヒドロキシアルキル化合物、又はそれらの二種類以上
の混合物から製造することができる。最も商業的に入手
することができるアルコールは純粋な化合物ではなく、
大部分が希望のアルコールで、少量の種々の異性体及び
（又は）一層長い又は短い鎖のアルコールを含む混合物
であることは理解されるべきである。Mixtures of hydroxyalkyl compounds can also be used. As recognized in the art, these hydroxyalkyl compounds need not be monohydroxyalkyl compounds. That is, dialkyldithiophosphoric acids can be prepared from mono-, di-, tri-, tetra-, and other poly-hydroxyalkyl compounds, or mixtures of two or more thereof. The most commercially available alcohols are not pure compounds,
It is to be understood that the mixture is predominantly the desired alcohol, with small amounts of various isomers and / or longer or shorter chain alcohols.

【００３０】式ＲＯＨ又はＲ′ＯＨに相当する一般的種
類の化合物の例は、Ｒ又はＲ′が、アルキル、シクロア
ルキル、アルキル置換シクロアルキル、アルコキシアル
キル、ハロアルキル等から選択されたものである化合物
である。そのようなヒドロキシアルキル化合物の特別な
例は、４−メチル−２−ペンタノール、２−ブタノー
ル、オクチルアルコール、シクロヘキサノール、２−エ
チル−ヘキサノール、イソプロパノール、メチルシクロ
ヘキサノール、シクロヘプタノール、シクロペンタノー
ル、ブタノール、イソアミルアルコール、オレイルアル
コール、ドデカノール、ラウリルアルコール、セチルア
ルコール、エチレングリコール、プロピレングリコー
ル、オクチルフェノキシエタノール、ネオペンチルアル
コール、イソヘキシルアルコール、２，３−ジメチルブ
タノール、ｎ−ヘプタノール、ジイソプロピルカルビノ
ール、グリセロール、ジエチレングリコール、カプリル
アルコール等である。Examples of compounds of the general class corresponding to the formula ROH or R'OH are compounds wherein R or R 'is selected from alkyl, cycloalkyl, alkyl-substituted cycloalkyl, alkoxyalkyl, haloalkyl and the like. It is. Particular examples of such hydroxyalkyl compounds are 4-methyl-2-pentanol, 2-butanol, octyl alcohol, cyclohexanol, 2-ethyl-hexanol, isopropanol, methylcyclohexanol, cycloheptanol, cyclopentanol , Butanol, isoamyl alcohol, oleyl alcohol, dodecanol, lauryl alcohol, cetyl alcohol, ethylene glycol, propylene glycol, octylphenoxyethanol, neopentyl alcohol, isohexyl alcohol, 2,3-dimethylbutanol, n-heptanol, diisopropylcarbinol, glycerol , Diethylene glycol, caprylic alcohol and the like.

【００３１】本発明のジアルキルジチオ燐酸形成段階で
用いられる五硫化燐反応物は、Ｐ2Ｓ3 、Ｐ4 Ｓ3 、Ｐ
4 Ｓ7 、又はＰ4 Ｓ9 の一種類以上を少量含んでいても
よい。そのような硫化燐組成物は少量の遊離硫黄を含ん
でいてもよい。The phosphorus pentasulfide reactants used in the dialkyldithiophosphoric acid forming step of the present invention include P 2 S 3 , P 4 S 3 , P
4 S 7, or may contain minor amounts of one or more of P 4 S 9. Such a phosphorus sulfide composition may contain small amounts of free sulfur.

【００３２】五硫化燐の構造は、一般にＰ2 Ｓ5 として
表されているが、実際の構造は４個の燐原子と１０個の
硫黄原子、即ち、Ｐ4 Ｓ10を含むものと考えられてい
る。本発明の目的にとって、硫化燐反応物は、Ｐ2 Ｓ5
の構造を有する化合物として考えるが、実際の構造は恐
らくＰ4 Ｓ10であると理解されている。The structure of phosphorus pentasulfide is generally represented as P 2 S 5 , but the actual structure is believed to contain four phosphorus atoms and ten sulfur atoms, ie, P 4 S 10. ing. For the purposes of the present invention, the phosphorus sulfide reactant is P 2 S 5
Is considered to be a compound having the structure of, but the actual structure is probably understood to be P 4 S 10 .

【００３３】潤滑油組成物 本発明の超中性ジアルキルジチオ燐酸亜鉛は、潤滑油に
摩耗防止性を与える潤滑油添加剤として有用である。そ
のような潤滑油組成物は、船舶エンジンと同様、ディー
ゼルエンジン、ガソリンエンジンに有用である。Lubricating Oil Composition The super-neutral zinc dialkyldithiophosphate of the present invention is useful as a lubricating oil additive that imparts anti-wear properties to lubricating oils. Such lubricating oil compositions are useful for diesel engines and gasoline engines as well as marine engines.

【００３４】そのような潤滑油組成物は、シングル又は
マルチグレードでもよい仕上げ潤滑油を用いている。マ
ルチグレード潤滑油は、粘度指数（ＶＩ）改良剤を添加
することにより調製されている。Such lubricating oil compositions employ a finished lubricating oil which may be single or multi-grade. Multigrade lubricating oils have been prepared by adding viscosity index (VI) improvers.

【００３５】そのような組成物に用いられる潤滑油、即
ち基礎油は、船舶エンジンを含めたガソリンエンジン及
びディーゼルエンジンのような内燃機関のクランクケー
スに用いるのに適した粘度の鉱油又は合成油でもよい。
クランクケース潤滑油は、通常、０°Ｆで約１３００ｃ
Ｓｔから９９℃（２１０°Ｆ）で２４ｃＳｔの粘度を有
する。潤滑油は、合成又は天然原料から誘導することが
できる。本発明の基礎油として用いられる鉱油には、パ
ラフィン系、ナフテン系、及び潤滑油組成物に通常用い
られている他の油が含まれる。合成油には、炭化水素合
成油及び合成エステルの両方が含まれる。有用な合成炭
化水素油には、適当な粘度を有するα−オレフィンの液
体重合体が含まれる。特に有用なものは、１−デセント
リマーのようなＣ6 〜Ｃ12αオレフィンの水素化液体オ
リゴマーである。同様に、ジドデシルベンゼンのような
適当な粘度のアルキルベンゼンを用いることもできる。
有用な合成エステルには、モノヒドロキシアルカノール
及びポリオールと同様、モノカルボン酸及びポリカルボ
ン酸の両方のエステルが含まれる。典型的な例は、アジ
ピン酸ジドデシル、テトラカプロン酸ペンタエリトリト
ール、アジピン酸ジ−２−エチルヘキシル、セバシン酸
ジラウリル等である。モノ及びジカルボン酸及びモノ及
びジヒドロキシアルカノールの混合物から調製された複
雑なエステルも用いることができる。The lubricating oil or base oil used in such compositions may be a mineral or synthetic oil of viscosity suitable for use in crankcases of internal combustion engines such as gasoline and diesel engines, including marine engines. Good.
Crankcase lubrication oil is typically about 1300c at 0 ° F
It has a viscosity of 24 cSt from St to 99 ° C. (210 ° F.). Lubricating oils can be derived from synthetic or natural sources. Mineral oils used as base oils in the present invention include paraffinic, naphthenic, and other oils commonly used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of α-olefins having suitable viscosities. Particularly useful are C 6 -C 12 alpha olefins hydrogenated liquid oligomers such as 1-decene trimer. Similarly, alkyl benzenes of suitable viscosity, such as didodecyl benzene, can be used.
Useful synthetic esters include esters of both monocarboxylic and polycarboxylic acids, as well as monohydroxyalkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilauryl sebacate and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used.

【００３６】炭化水素油と合成油との混合物も有用であ
る。例えば、１０〜２５重量％の水素化１−デセントリ
マーと、７５〜９０重量％の１５０ＳＵＳ（１００°
Ｆ）鉱油との混合物は、優れた潤滑基礎油を与える。[0036] Mixtures of hydrocarbon oils and synthetic oils are also useful. For example, 10-25% by weight of hydrogenated 1-centrifuge and 75-90% by weight of 150 SUS (100 °
F) Mixture with mineral oil gives an excellent lubricating base oil.

【００３７】潤滑油組成物は、少量の無灰分散剤、フェ
ネート及びスルホネート清浄剤、防錆剤、消泡剤、防腐
剤、金属不活性化剤、流動点降下剤、酸化防止剤、及び
種々の他のよく知られた添加剤を含んでいてもよい。The lubricating oil composition comprises a small amount of ashless dispersants, phenate and sulfonate detergents, rust inhibitors, defoamers, preservatives, metal deactivators, pour point depressants, antioxidants, and various Other well-known additives may be included.

【００３８】無灰分散剤 本発明で有用な無灰分散剤の例には、スクシンイミド及
びスクシンエステルで、その各々が約７００〜３，００
０の分子量のアルキル又はアルケニル基を有するものが
含まれる。これらの化合物の外に、それらの誘導体（例
えば、硼酸化誘導体）も用いることができる。無灰分散
剤は、一般にエンジンオイルの全量につき、０〜２０重
量％、好ましくは１〜１０重量％の量でエンジンオイル
中に配合される。Ashless Dispersants Examples of ashless dispersants useful in the present invention are succinimides and succinesters, each of which is about 700-3,000.
Those having an alkyl or alkenyl group having a molecular weight of 0 are included. In addition to these compounds, their derivatives (for example, borated derivatives) can also be used. Ashless dispersants are generally incorporated into engine oils in amounts of 0 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of engine oil.

【００３９】過塩基性硫化アルキルフェネート 本発明で有用な過塩基性硫化アルキルフェネートの例に
は、例えば、米国特許第２，６８０，０９６号、第３，
１７８，３６８号、第３，３６７，８６７号、第３，８
０１，５０７号、第５，５２９，７０５号明細書等（そ
れらは全ての目的に対し、参考のため全てここに入れて
ある）に記載されているものが含まれる。過塩基性硫化
アルキルフェネートは、一般にエンジンオイルの全量に
つき、０〜２０重量％、好ましくは１〜１０重量％の量
でエンジンオイルに配合される。Examples of overbased sulfurized alkyl phenates useful in the present invention include, for example, US Pat. Nos. 2,680,096 and 3,
No. 178,368, No. 3,367,867, No. 3,8
No. 01,507, 5,529,705, etc. (all of which are incorporated herein by reference for all purposes). The overbased sulfurized alkyl phenate is generally incorporated into the engine oil in an amount of 0 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the engine oil.

【００４０】酸化防止剤本発明で有用な酸化防止剤の例
には、フェノール型（フェノール系）酸化防止剤、例え
ば、４，４′−メチレン−ビス（２，６−ジ−ｔ−ブチ
ルフェノール）、４，４′−ビス（２，６−ジ−ｔ−ブ
チルフェノール）、４，４′−ビス（２−メチル−６−
ｔ−ブチルフェノール）、２，２′−メチレン−ビス
（４−メチル−６−ｔ−ブチルフェノール）、４，４′
−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェ
ノール）、４，４′−イソプロピリデン−ビス（２，６
−ジ−ｔ−ブチルフェノール）、２，２′−メチレン−
ビス（４−メチル−６−ノニルフェノール）、２，２′
−イソブチリデン−ビス（４，６−ジメチルフェノー
ル）、２，２′−メチレン−ビス（４−メチル−６−シ
クロヘキシルフェノール）、２，６−ジ−ｔ−ブチル−
４−メチルフェノール、２，６−ジ−ｔ−ブチル−４−
エチルフェノール、２，４−ジメチル−６−ｔ−ブチル
フェノール、２，６−ジ−ｔ−α−ジメチルアミノ−ｐ
−クレゾール、２，６−ジ−ｔ−４−（Ｎ, Ｎ′−ジメ
チル−アミノメチルフェノール）、４，４′−チオビス
（２−メチル−６−ｔ−ブチルフェノール）、２，２′
−チオビス（４−メチル−６−ｔ−ブチルフェノー
ル）、ビス（３−メチル−４−ヒドロキシ−５−ｔ−ブ
チルベンジル）−スルフィド、及びビス（３，５−ジ−
ｔ−ブチル−４−ヒドロキシベンジル）が含まれるが、
それらに限定されるものではない。ジフェニルアミン型
酸化防止剤には、アルキル化ジフェニルアミン、フェニ
ル−α−ナフチルアミン、及びアルキル化α−ナフチル
アミンが含まれるが、それらに限定されるものではな
い。酸化防止剤の他の型のものには、金属ジチオカルバ
ミン酸塩（例えば、ジチオカルバミン酸亜鉛）、及びメ
チレンビス（ジブチルジチオカルバメート）が含まれ
る。酸化防止剤は、一般にエンジンオイルの全量につ
き、０〜１０重量％、好ましくは０．０５〜２重量％の
量でエンジンオイルに配合される。Antioxidants Examples of antioxidants useful in the present invention include phenolic (phenolic) antioxidants such as 4,4'-methylene-bis (2,6-di-t-butylphenol). , 4,4'-bis (2,6-di-t-butylphenol), 4,4'-bis (2-methyl-6-
t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4 '
-Butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-isopropylidene-bis (2,6
-Di-t-butylphenol), 2,2'-methylene-
Bis (4-methyl-6-nonylphenol), 2,2 '
-Isobutylidene-bis (4,6-dimethylphenol), 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,6-di-t-butyl-
4-methylphenol, 2,6-di-t-butyl-4-
Ethylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-α-dimethylamino-p
-Cresol, 2,6-di-t-4- (N, N'-dimethyl-aminomethylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 2,2 '
-Thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) -sulfide, and bis (3,5-di-
t-butyl-4-hydroxybenzyl),
It is not limited to them. Diphenylamine-type antioxidants include, but are not limited to, alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated α-naphthylamine. Other types of antioxidants include metal dithiocarbamates (eg, zinc dithiocarbamate), and methylene bis (dibutyldithiocarbamate). The antioxidant is generally incorporated into the engine oil in an amount of 0 to 10% by weight, preferably 0.05 to 2% by weight based on the total amount of the engine oil.

【００４１】粘度指数改良剤 本発明で有用な粘度指数改良剤の例には、ポリ（アルキ
ルメタクリレート）、エチレン・プロピレン共重合体、
スチレン・ブタジエン共重合体、及びポリイソプレンが
含まれる。分散剤型（大きな分散性を有する）又は多官
能型の粘度指数改良剤も用いられる。これらの粘度指数
改良剤は、単独又は組合せて用いることができる。粘度
指数改良剤は、一般にエンジンオイルの全量につき、０
〜２０重量％、好ましくは１〜１５重量％の量でエンジ
ンオイルに配合される。Examples of viscosity index improvers useful in the present invention include poly (alkyl methacrylate), ethylene / propylene copolymer,
Styrene-butadiene copolymer and polyisoprene are included. Dispersant type (having large dispersibility) or polyfunctional type viscosity index improvers are also used. These viscosity index improvers can be used alone or in combination. Viscosity index improvers are generally present in an amount of 0 per engine oil.
It is incorporated into the engine oil in an amount of -20% by weight, preferably 1-15% by weight.

【００４２】潤滑油組成物は、主成分量の潤滑粘度の基
礎油、０〜２０重量％の無灰分散剤、０〜２０重量％の
過塩基性硫化アルキルフェネート清浄剤、０〜１０重量
％の酸化防止剤、０〜２０重量％の粘度指数改良剤、及
び０．０５〜５重量％のジアルキルジチオ燐酸亜鉛で、
０．９５：１〜１．０４：１の範囲の亜鉛対燐重量比を
有するジアルキルジチオ燐酸亜鉛を一緒に混合すること
により製造することができ、然も、前記潤滑油組成物の
灰分含有量は１．５重量％より少ない。この方法により
製造された潤滑油組成物は、それら成分が相互作用を及
ぼすため、僅かに異なった組成を持っていてもよい。The lubricating oil composition comprises a base oil of a base oil of lubricating viscosity, 0-20% by weight of an ashless dispersant, 0-20% by weight of an overbased sulfurized alkylphenate detergent, 0-10% by weight An antioxidant, 0 to 20% by weight of a viscosity index improver, and 0.05 to 5% by weight of a zinc dialkyldithiophosphate,
The ash content of the lubricating oil composition can be prepared by mixing together zinc dialkyldithiophosphates having a zinc to phosphorus weight ratio ranging from 0.95: 1 to 1.04: 1. Is less than 1.5% by weight. Lubricating oil compositions made by this method may have slightly different compositions because the components interact.

【００４３】[0043]

【実施例】本発明を、特に有利な方法の態様を記載した
次の実施例により更に例示する。実施例は本発明を例示
するために与えられているが、それらは本発明を限定す
るものではない。The invention is further illustrated by the following examples, which describe particularly advantageous method embodiments. The examples are given to illustrate the invention, but they do not limit the invention.

【００４４】例１ 超中性ジアルキルジチオ燐酸亜鉛塩の製造 超中性ジアルキルジチオ燐酸亜鉛塩を、１分子当たり平
均約４．５の炭素を有する第二級アルコール混合物から
アルキル基が誘導されているジアルキルジチオ燐酸から
次の方法により製造した。１１６４ｇの１００中性油、
８．７ｇの酢酸、及び全ジアルキルジチオ燐酸導入量の
約2/3 （２０３４ｇ）を撹拌丸底ガラスフラスコ中へ入
れた。次に４３７ｇの酸化亜鉛を、その反応混合物中へ
入れた。残りのジアルキルジチオ燐酸（１０１７ｇ）
を、混合物の温度が７７℃を越えないような速度で添加
した。全てのジアルキルジチオ燐酸が添加した後、反応
混合物の温度を約７７℃に３時間維持した。３時間後、
反応混合物を９９℃へ加熱し、３０分間真空を適用し、
全ての水及び（又は）未反応アルコールを除去した。珪
藻土フィルター助剤を用いて生成物を濾過した。この物
質の亜鉛及び燐の含有量を測定し、計算により亜鉛対燐
比は０．９８であることが分かった。31Ｐ ＮＭＲによ
り塩基性塩は検出されなかった。Example 1 Preparation of a super-neutral zinc dialkyldithiophosphate. A super-neutral zinc dialkyldithiophosphate is obtained by deriving an alkyl group from a mixture of secondary alcohols having an average of about 4.5 carbons per molecule. It was prepared from dialkyldithiophosphoric acid by the following method. 1164 g of 100 neutral oils,
8.7 g of acetic acid and about 2/3 (2034 g) of the total introduced dialkyldithiophosphoric acid were placed in a stirred round bottom glass flask. Next, 437 g of zinc oxide was charged into the reaction mixture. Remaining dialkyldithiophosphoric acid (1017 g)
Was added at such a rate that the temperature of the mixture did not exceed 77 ° C. After all the dialkyldithiophosphoric acid was added, the temperature of the reaction mixture was maintained at about 77 ° C. for 3 hours. Three hours later,
Heating the reaction mixture to 99 ° C. and applying vacuum for 30 minutes;
All water and / or unreacted alcohol was removed. The product was filtered using diatomaceous earth filter aid. The zinc and phosphorus content of this material was measured and calculated to show a zinc to phosphorus ratio of 0.98. No basic salt was detected by 31 P NMR.

【００４５】例２ 塩基性ジアルキルジチオ燐酸亜鉛塩と超中性ジアルキル
ジチオ燐酸亜鉛塩の比較 塩基性と超中性のジアルキルジチオ燐酸亜鉛塩を、例１
に示したのとは異なった方法を用いて合成した。各塩
を、次のものを含む油配合物中へ混合した：グループ１
基礎材料、８重量％の無灰分散剤、５３ｍＭ／ｋｇの金
属分散剤、０．２重量％の酸化防止剤、及びＳＡＥ１５
Ｗ−４０等級潤滑油を達成するための非分散剤オレフィ
ン共重合体粘度指数改良剤。これらの油をＡＳＴＭシー
クエンス(Sequence)ＶＥエンジン試験で試験し、この場
合フォード(Ford)２．３リットル４気筒エンジンを用い
た。この試験方法は、低速、低温度「停止及び発進」市
内走行及び中程度高速道路走行の組合せを特徴とする厳
しい実地試験型操作に類似していた。油中の添加剤の効
果性は、バルブ列摩耗に対して与えられる保護に関して
測定した。シークエンスＶＥ摩耗試験結果を表１に示
す。Example 2 Comparison of Basic Zinc Dialkyldithiophosphate and Super Neutral Dialkyldithiophosphate Zinc Basic and superneutral zinc dialkyldithiophosphates were prepared in Example 1
The synthesis was performed using a different method from that shown in Table 1. Each salt was mixed into an oil formulation containing: Group 1
Base material, 8 wt% ashless dispersant, 53 mM / kg metal dispersant, 0.2 wt% antioxidant, and SAE15
Non-dispersant olefin copolymer viscosity index improver to achieve W-40 grade lubricating oil. These oils were tested in the ASTM Sequence VE engine test, using a Ford 2.3 liter 4-cylinder engine. This test method was similar to a rigorous field-test-type operation featuring a combination of low speed, low temperature "stop and start" city driving and moderate highway driving. The effectiveness of the additives in the oil was measured in terms of the protection provided against valve row wear. Table 1 shows the results of the sequence VE wear test.

【００４６】[0046]

【表１】 表Ｉ． シークエンスＶＥエンジン試験での超中性ＺｎＤＴＰ対 塩基性ＺｎＤＴＰ摩耗性能 Ｚｎ：Ｐ比 カム平均摩耗 カム最大摩耗 塩基性塩ＺｎＤＴＰ 1.27:1 7.62±4.02 17.2±3.75 超中性塩ＺｎＤＴＰ 0.98:1 0.81±0.94 3.83±5.86Table I. Ultra-neutral ZnDTP versus basic ZnDTP wear performance in sequence VE engine test Zn: P ratio Cam average wear cam Maximum wear basic salt ZnDTP 1.27: 1 7.62 ± 4.02 17.2 ± 3.75 Super-neutral salt ZnDTP 0.98: 1 0.81 ± 0.94 3.83 ± 5.86

【００４７】データーは、超中性ジアルキルジチオ燐酸
亜鉛塩は、これらの試験条件下で、平均カム摩耗及び最
大カム摩耗により測定して、塩基性ジアルキルジチオ燐
酸亜鉛塩よりも良好な摩耗性能を与えたことを示してい
る。表II及びIII はエンジン試験データーの統計分析を
示している。これらの分析値は、この摩耗データーに高
いレベルの信頼性が存在することを示している。The data show that ultra neutral zinc dialkyldithiophosphates give better wear performance than basic zinc dialkyldithiophosphates under these test conditions, as measured by average cam wear and maximum cam wear. It shows that. Tables II and III show the statistical analysis of the engine test data. These analyzes indicate that there is a high level of confidence in the wear data.

【００４８】[0048]

【表２】 表II．シークエンスＶＥ摩耗性能の統計分析 〔平均カム摩耗（ＡＣＷ）の平方根〕 亜鉛の種類 ｎ 平均 ｐ−値（結論） 塩基性塩ＺｎＤＴＰ ３ 2.68 0.027 （有意差） 超中性塩ＺｎＤＴＰ ３ 0.80[Table 2] Table II. Statistical analysis of sequence VE wear performance [Square root of average cam wear (ACW)] zinc type n average p-value (conclusion) basic salt ZnDTP 3 2.68 0.027 (significant difference) super neutral salt ZnDTP 30.80

【００４９】ＺｎＤＴＰの種類：ＡＣＷの平方根には、
平均ジアルキルジチオ燐酸亜鉛の種類による統計的な有
意差がある（ｐ＝０．０２７、信頼レベル９７．３％）Types of ZnDTP: The square root of ACW is:
There is a statistically significant difference depending on the type of average zinc dialkyldithiophosphate (p = 0.027, confidence level 97.3%)

【００５０】[0050]

【表３】 表III ．シークエンスＶＥ摩耗性能の統計分析 〔最大カム摩耗（ＭＣＷ）の平方根〕 亜鉛の種類 ｎ 平均 ｐ−値（結論） 塩基性塩ＺｎＤＴＰ ３ 4.13 0.045 （有意差） 超中性塩ＺｎＤＴＰ ３ 1.53Table 3 Table III. Statistical analysis of sequence VE wear performance [Square root of maximum cam wear (MCW)] Type of zinc n- average p-value (conclusion) Basic salt ZnDTP 3 4.13 0.045 (significant difference) Super neutral salt ZnDTP 3 1.53

【００５１】ＺｎＤＴＰの種類：ＭＣＷの平方根の平均
には、ジアルキルジチオ燐酸亜鉛の種類による統計的な
有意差がある（ｐ＝０．０４５、信頼レベル９５．５
％）Type of ZnDTP: The mean square root of MCW has a statistically significant difference depending on the type of zinc dialkyldithiophosphate (p = 0.045, confidence level 95.5).
%)

【００５２】例３ 超中性ジアルキルジチオ燐酸亜鉛塩腐食試験結果 超中性ジアルキルジチオ燐酸亜鉛塩を、１分子当たり平
均約４．５個の炭素を有する第二級アルコール混合物か
らアルキル基が誘導されているジアルキルジチオ燐酸か
ら製造した。誘導された超中性ジアルキルジチオ燐酸亜
鉛は、０．９８：１のＺｎ：Ｐ比を持っており、それは
中性ジアルキルジチオ燐酸亜鉛の理論的１．０５：１よ
りも小さく、炭素鋼に対し低い腐食性を持つことが判明
した。EXAMPLE 3 Results of Corrosion Test of Zinc Super Neutral Dialkyldithiophosphate Phosphate salt of ultraneutral dialkyldithiophosphate was obtained by deriving an alkyl group from a mixture of secondary alcohols having an average of about 4.5 carbons per molecule. Prepared from dialkyldithiophosphoric acid. The derived super-neutral zinc dialkyldithiophosphate has a Zn: P ratio of 0.98: 1, which is less than the theoretical 1.05: 1 of neutral zinc dialkyldithiophosphate and for carbon steel It was found to have low corrosivity.

【００５３】腐食試験は次のようにして行われた：約２
×２ｉｎ四方の新しい炭素鋼（１０１８型）の三つの試
験片を、小数点以下４桁まで夫々秤量した。それら試験
片を完全に浸漬するのに充分な第二級ジアルキルジチオ
燐酸亜鉛の入ったガラス容器中に、試験片をテフロンテ
ープで吊るした。この第二級ジアルキルジチオ燐酸亜鉛
は、０．９８：１の亜鉛対燐比をもち、31Ｐ ＮＭＲ分
析により塩基性を含んでいなかった。試験片及びジアル
キルジチオ燐酸亜鉛を入れた容器を５２℃のオーブンへ
入れた。第一の試験片を、検査するため７２時間後に試
験液から取り出した。形成されたスールを除去するた
め、それをクレンザーを用いて穏やかに清浄にした。次
にそれを水で濯ぎ、メタノール中で５分間超音波にかけ
た。清浄にした試験片を、次に１００°Ｆのオーブンで
乾燥した。試験片を秤量し、重量損失及び露出時間に基
づいて腐食速度を計算し、０．６２ミル／年であること
が分かった。第二の試験片を１９８時間後に取り出し
た。前に述べた方法を用いてそれを清浄にした。この試
験片について測定した腐食速度は、０．２７ミル／年で
あった。第三の試験片を７２０時間後に取り出し、前に
述べた清浄化法を用いてそれを清浄にした。この試験片
について測定した腐食速度は０．０５ミル／年であっ
た。試験結果を表IVに示す。The corrosion test was performed as follows: about 2
Three test pieces of new carbon steel (type 1018) of × 2 in square were weighed to four decimal places. The specimens were suspended with Teflon tape in a glass container containing sufficient zinc secondary dialkyldithiophosphate to completely immerse the specimens. The zinc secondary dialkyldithiophosphate had a zinc to phosphorus ratio of 0.98: 1 and was free of basicity by 31 P NMR analysis. The container containing the test specimen and the zinc dialkyldithiophosphate was placed in a 52 ° C. oven. The first test strip was removed from the test solution after 72 hours for inspection. It was gently cleaned with a cleanser in order to remove the formed sour. It was then rinsed with water and sonicated in methanol for 5 minutes. The cleaned specimen was then dried in a 100 ° F. oven. The specimen was weighed and the corrosion rate was calculated based on the weight loss and exposure time and found to be 0.62 mil / year. A second specimen was removed after 198 hours. It was cleaned using the method described previously. The corrosion rate measured on this specimen was 0.27 mil / year. A third coupon was removed after 720 hours and it was cleaned using the cleaning method described previously. The corrosion rate measured on this specimen was 0.05 mil / year. The test results are shown in Table IV.

【００５４】[0054]

【表４】 表IV．超中性塩／炭素鋼腐食試験結果 腐食速度 ＮＭＲによる 露出温度 （ミル／年） Ｚｎ：Ｐ 塩基性塩％ （℃） 72時間後 198 時間後 720 時間後 0.98 0.0 52 0.62 0.27 0.05Table IV. Ultra neutral salt / carbon steel corrosion test result Corrosion rate Exposure temperature by NMR (mil / year) Zn: P basic salt% (° C) After 72 hours 198 hours After 720 hours 0.98 0.0 52 0.62 0.27 0.05

【００５５】例４ 超中性ジアルキルジチオ燐酸亜鉛塩についての粗沈澱物 １．０５：１より低いＺｎ：Ｐ比を有するジアルキルジ
チオ燐酸亜鉛の製造工程中に生ずる沈澱物は、一層大き
なＺｎ：Ｐ比を有するジアルキルジチオ燐酸亜鉛が製造
された場合よりも少ない傾向がある。Example 4 Crude Precipitate for Ultra-Neutral Zinc Dialkyldithiophosphate Salt The precipitate formed during the process of producing zinc dialkyldithiophosphate having a Zn: P ratio of less than 1.05: 1 is greater Zn: P Zinc dialkyldithiophosphates having a ratio tend to be less than if produced.

【００５６】超中性第二級ジアルキルジチオ燐酸亜鉛塩
を、次のようにして製造した。１２４．９ｇの１００中
性油、１．０ｇの酢酸、及び全ジアルキルジチオ燐酸導
入量の約2/3 （２１８．３ｇ）を撹拌丸底ガラスフラス
コ中へ入れた。次に４８．４ｇの酸化亜鉛を反応混合へ
導入した。残りのジアルキルジチオ燐酸（１０９．２
ｇ）を、混合物の温度が７７℃を越えないような速度で
添加した。全てのジアルキルジチオ燐酸を添加した後、
反応混合物の温度を約７７℃に３時間保持した。３時間
後、反応混合物を約９７℃に加熱し、真空を３０分間適
用して全ての水及び（又は）未反応アルコールを除去し
た。生成物をヘキサンで希釈し、遠心分離にかけ、全て
の沈澱物を分離した。沈澱物からヘキサン溶液を傾瀉し
て除去し、廃棄した。沈澱物をヘキサンで洗浄し、再び
遠心分離にかけ、液体を傾瀉して除去した。この洗浄法
を繰り返した。沈澱物を乾燥し、秤量した。沈澱物は
０．０５重量％であることが決定された。この物質の亜
鉛及び燐含有量を測定し、亜鉛対燐比は計算により１．
０１：１であることが分かった。塩基性塩は31Ｐ ＮＭ
Ｒにより検出されなかった。An ultra-neutral secondary zinc dialkyldithiophosphate was prepared as follows. 124.9 g of 100 neutral oil, 1.0 g of acetic acid, and about 2/3 (218.3 g) of total dialkyldithiophosphoric acid introduction were charged into a stirred round bottom glass flask. Next, 48.4 g of zinc oxide was introduced into the reaction mixture. The remaining dialkyldithiophosphoric acid (109.2
g) was added at such a rate that the temperature of the mixture did not exceed 77 ° C. After adding all the dialkyldithiophosphoric acid,
The temperature of the reaction mixture was maintained at about 77 ° C. for 3 hours. After 3 hours, the reaction mixture was heated to about 97 ° C. and vacuum was applied for 30 minutes to remove any water and / or unreacted alcohol. The product was diluted with hexane and centrifuged to separate any precipitate. The hexane solution was decanted off from the precipitate and discarded. The precipitate was washed with hexane, centrifuged again, and the liquid was decanted off. This washing procedure was repeated. The precipitate was dried and weighed. The precipitate was determined to be 0.05% by weight. The zinc and phosphorus content of this material was measured and the zinc to phosphorus ratio was calculated to be 1.
01: 1 was found. Basic salt is 31 P NM
Not detected by R.

【００５７】比較例４Ａ 中性ジアルキルジチオ燐酸亜鉛塩についての粗沈澱物 例４で用いたのと同じジアルキルジチオ燐酸を用いて、
第二級ジアルキルジチオ燐酸亜鉛塩を別に次のようにし
て製造した。１２８．２ｇの１００中性油、１．０ｇの
酢酸、及び全ジアルキルジチオ燐酸導入量の約2/3 （２
２４．１ｇ）を撹拌丸底ガラスフラスコ中へ入れた。次
に５１．７ｇの酸化亜鉛を反応混合へ導入した。残りの
ジアルキルジチオ燐酸（１１２．１ｇ）を、混合物の温
度が７７℃を越えないような速度で添加した。全てのジ
アルキルジチオ燐酸を添加したならば、反応混合物の温
度を約７７℃に３時間保持した。３時間後、反応混合物
を約９７℃に加熱し、真空を３０分間適用して全ての水
及び（又は）未反応アルコールを除去した。生成物をヘ
キサンで希釈し、遠心分離にかけ、全ての沈澱物を分離
した。沈澱物からヘキサン溶液を傾瀉して除去した。沈
澱物をヘキサンで洗浄し、再び遠心分離にかけ、液体を
傾瀉して除去した。この洗浄法を繰り返した。沈澱物は
０．０４重量％であることが決定された。この物質の亜
鉛及び燐含有量を測定し、亜鉛対燐比は計算により１．
０６であることが分かった。この物質は、31Ｐ ＮＭＲ
により決定して、１４重量％（全中性及び塩基性塩基
準）の塩基性塩を含んでいた。COMPARATIVE EXAMPLE 4A Crude Precipitate for Neutral Zinc Dialkyldithiophosphate Using the same dialkyldithiophosphoric acid used in Example 4,
A secondary zinc dialkyldithiophosphate was prepared separately as follows. 128.2 g of 100 neutral oil, 1.0 g of acetic acid, and about 2/3 of the total amount of dialkyldithiophosphoric acid introduced (2
24.1 g) was placed in a stirred round bottom glass flask. Next, 51.7 g of zinc oxide was introduced into the reaction mixture. The remaining dialkyldithiophosphoric acid (112.1 g) was added at a rate such that the temperature of the mixture did not exceed 77 ° C. Once all the dialkyldithiophosphoric acid was added, the temperature of the reaction mixture was maintained at about 77 ° C for 3 hours. After 3 hours, the reaction mixture was heated to about 97 ° C. and vacuum was applied for 30 minutes to remove any water and / or unreacted alcohol. The product was diluted with hexane and centrifuged to separate any precipitate. The hexane solution was decanted from the precipitate. The precipitate was washed with hexane, centrifuged again, and the liquid was decanted off. This washing procedure was repeated. The precipitate was determined to be 0.04% by weight. The zinc and phosphorus content of this material was measured and the zinc to phosphorus ratio was calculated to be 1.
06. This material has a 31 P NMR
14% by weight (based on total neutral and basic salts) as determined by HPLC.

【００５８】比較例４Ｂ 塩基性ジアルキルジチオ燐酸亜鉛塩についての粗沈澱物 例４で用いたのと同じジアルキルジチオ燐酸を用いて、
第二級ジアルキルジチオ燐酸亜鉛塩を別に次のようにし
て製造した。９５．１ｇの１００中性油、０．８ｇの酢
酸、及び全ジアルキルジチオ燐酸導入量の約2/3 （１６
６．３ｇ）を撹拌丸底ガラスフラスコ中へ入れた。次に
３９．９ｇの酸化亜鉛を反応混合へ導入した。残りのジ
アルキルジチオ燐酸（８３．１ｇ）を、混合物の温度が
７７℃を越えないような速度で添加した。全てのジアル
キルジチオ燐酸を添加した後、反応混合物の温度を約７
７℃に３時間保持した。３時間後、反応混合物を約９８
℃に加熱し、真空を３０分間適用して全ての水及び（又
は）未反応アルコールを除去した。生成物をヘキサンで
希釈し、遠心分離にかけ、全ての沈澱物を分離した。沈
澱物からヘキサン溶液を傾瀉して除去した。沈澱物をヘ
キサンで洗浄し、再び遠心分離にかけ、液体を傾瀉して
除去した。この洗浄法を繰り返した。沈澱物を乾燥し、
秤量した。沈澱物は０．０９重量％であることが決定さ
れた。この物質の亜鉛及び燐含有量を測定し、亜鉛対燐
比は計算により１．０９であることが分かった。この物
質は、31Ｐ ＮＭＲにより決定して、２２重量％（全中
性及び塩基性塩基準）の塩基性塩を含んでいた。Comparative Example 4B Crude Precipitate for Basic Zinc Dialkyldithiophosphate Using the same dialkyldithiophosphoric acid used in Example 4,
A secondary zinc dialkyldithiophosphate was prepared separately as follows. 95.1 g of 100 neutral oil, 0.8 g of acetic acid, and about 2/3 (16
6.3 g) was placed in a stirred round bottom glass flask. Next, 39.9 g of zinc oxide was introduced into the reaction mixture. The remaining dialkyldithiophosphoric acid (83.1 g) was added at such a rate that the temperature of the mixture did not exceed 77 ° C. After all the dialkyldithiophosphoric acid has been added, the temperature of the reaction mixture is reduced to about 7
It was kept at 7 ° C. for 3 hours. After 3 hours, the reaction mixture was
Heated to ° C. and applied vacuum for 30 minutes to remove any water and / or unreacted alcohol. The product was diluted with hexane and centrifuged to separate any precipitate. The hexane solution was decanted from the precipitate. The precipitate was washed with hexane, centrifuged again, and the liquid was decanted off. This washing procedure was repeated. Drying the precipitate,
Weighed. The precipitate was determined to be 0.09% by weight. The zinc and phosphorus content of this material was measured and the zinc to phosphorus ratio was calculated to be 1.09. This material contained 22% by weight (based on total neutral and basic salts) of the basic salt as determined by 31 P NMR.

【００５９】比較例４Ｃ 塩基性ジアルキルジチオ燐酸亜鉛塩についての粗沈澱物 例４で用いたのと同じジアルキルジチオ燐酸を用いて、
第二級ジアルキルジチオ燐酸亜鉛塩を別に次のようにし
て製造した。９４．７ｇの１００中性油、０．８ｇの酢
酸、及び全ジアルキルジチオ燐酸導入量の約2/3 （１６
５．５ｇ）を撹拌丸底ガラスフラスコ中へ入れた。次に
４１．２ｇの酸化亜鉛を反応混合へ導入した。残りのジ
アルキルジチオ燐酸（８２．７ｇ）を、混合物の温度が
７７℃を越えないような速度で添加した。全てのジアル
キルジチオ燐酸を添加した後、反応混合物の温度を約７
７℃に３時間保持した。３時間後、反応混合物を約９９
℃に加熱し、真空を３０分間適用して全ての水及び（又
は）未反応アルコールを除去した。生成物をヘキサンで
希釈し、遠心分離にかけ、全ての沈澱物を分離した。沈
澱物からヘキサン溶液を傾瀉して除去した。沈澱物をヘ
キサンで洗浄し、再び遠心分離にかけ、液体を傾瀉して
除去した。この洗浄法を繰り返した。沈澱物を乾燥し、
秤量した。沈澱物は０．２８重量％であることが決定さ
れた。この物質の亜鉛及び燐含有量を測定し、亜鉛対燐
比は計算により１．１１であることが分かった。この物
質は、31Ｐ ＮＭＲにより決定して、２７重量％（全中
性及び塩基性塩基準）の塩基性塩を含んでいた。Comparative Example 4C Crude Precipitate for Basic Zinc Dialkyldithiophosphate Using the same dialkyldithiophosphoric acid used in Example 4,
A secondary zinc dialkyldithiophosphate was prepared separately as follows. 94.7 g of 100 neutral oil, 0.8 g of acetic acid and about 2/3 (16
5.5 g) was placed in a stirred round bottom glass flask. Next, 41.2 g of zinc oxide was introduced into the reaction mixture. The remaining dialkyldithiophosphoric acid (82.7 g) was added at such a rate that the temperature of the mixture did not exceed 77 ° C. After all the dialkyldithiophosphoric acid has been added, the temperature of the reaction mixture is reduced to about 7
It was kept at 7 ° C. for 3 hours. After 3 hours, the reaction mixture is
Heated to ° C. and applied vacuum for 30 minutes to remove any water and / or unreacted alcohol. The product was diluted with hexane and centrifuged to separate any precipitate. The hexane solution was decanted from the precipitate. The precipitate was washed with hexane, centrifuged again, and the liquid was decanted off. This washing procedure was repeated. Drying the precipitate,
Weighed. The precipitate was determined to be 0.28% by weight. The zinc and phosphorus content of this material was measured and the zinc to phosphorus ratio was calculated to be 1.11. This material contained 27% by weight (based on total neutral and basic salts) of the basic salt as determined by 31 P NMR.

【００６０】本発明を特定の態様に関して記述してきた
が、本願は、特許請求の範囲及びその本質から離れるこ
となく、当業者により行うことができるそれら種々の変
更及び置換を包含するものである。Although the invention has been described with respect to particular embodiments, this application is intended to cover those various changes and substitutions that can be made by those skilled in the art without departing from the scope and spirit of the claims.

Claims (12)

【特許請求の範囲】[Claims] 【請求項１】 （ａ） 潤滑粘度の基礎油、及び（ｂ）
０．９５：１〜１．０４：１の範囲の亜鉛対燐重量比
を有するジアルキルジチオ燐酸亜鉛、からなり、然も前
記潤滑油組成物の灰分含有量が１．５重量％より少ない
潤滑油組成物。1. A base oil of lubricating viscosity, and (b)
A lubricating oil comprising a zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio in the range of 0.95: 1 to 1.04: 1, wherein the ash content of the lubricating oil composition is less than 1.5% by weight Composition. 【請求項２】 潤滑油組成物の灰分含有量が１．１重量
％より少ない、請求項１に記載の潤滑油組成物。2. The lubricating oil composition according to claim 1, wherein the ash content of the lubricating oil composition is less than 1.1% by weight. 【請求項３】 潤滑油組成物の灰分含有量が１．０重量
％より少ない、請求項２に記載の潤滑油組成物。3. The lubricating oil composition according to claim 2, wherein the ash content of the lubricating oil composition is less than 1.0% by weight. 【請求項４】 ジアルキルジチオ燐酸亜鉛のアルキル基
の各々が、３〜２０個の炭素原子を有する、請求項３に
記載の潤滑油組成物。4. A lubricating oil composition according to claim 3, wherein each of the alkyl groups of the zinc dialkyldithiophosphate has from 3 to 20 carbon atoms. 【請求項５】 ジアルキルジチオ燐酸亜鉛のアルキル基
の各々が、３〜８個の炭素原子を有する、請求項４に記
載の潤滑油組成物。5. The lubricating oil composition according to claim 4, wherein each of the alkyl groups of the zinc dialkyldithiophosphate has from 3 to 8 carbon atoms. 【請求項６】 ジアルキルジチオ燐酸亜鉛のアルキル基
の各々が、第二級アルキル基である、請求項４に記載の
潤滑油組成物。6. The lubricating oil composition according to claim 4, wherein each of the alkyl groups of the zinc dialkyldithiophosphate is a secondary alkyl group. 【請求項７】 過塩基性硫化アルキルフェネート清浄剤
を更に含有する、請求項２に記載の潤滑油組成物。7. The lubricating oil composition of claim 2, further comprising an overbased sulfurized alkyl phenate detergent. 【請求項８】 （ａ） 主成分量の潤滑油粘度の基礎
油、 （ｂ） ０〜２０重量％の無灰分散剤、 （ｃ） ０〜２０重量％の過塩基性硫化アルキルフェネ
ート清浄剤、 （ｄ） ０〜１０重量％の酸化防止剤、 （ｅ） ０〜２０重量％の粘度指数改良剤、及び （ｆ） ０．０５〜５重量％のジアルキルジチオ燐酸亜
鉛で、０．９５：１〜１．０４：１の範囲の亜鉛対燐重
量比を有するジアルキルジチオ燐酸亜鉛、からなり、然
も、前記潤滑油組成物の灰分含有量が１．５重量％より
少ない潤滑油組成物。8. A base oil of lubricating oil viscosity of the main component amount, (b) 0 to 20% by weight of ashless dispersant, (c) 0 to 20% by weight of overbased sulfurized alkyl phenate detergent (D) 0-10% by weight antioxidant, (e) 0-20% by weight viscosity index improver, and (f) 0.05-5% by weight zinc dialkyldithiophosphate, 0.95: A lubricating oil composition comprising a zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio in the range of 1-1.04: 1, wherein the ash content of the lubricating oil composition is less than 1.5% by weight. 【請求項９】 （ａ） 主成分量の潤滑油粘度の基礎
油、 （ｂ） １〜１０重量％の無灰分散剤、 （ｃ） １〜１０重量％の過塩基性硫化アルキルフェネ
ート清浄剤、 （ｄ） ０．０５〜２重量％の酸化防止剤、 （ｅ） １〜１５重量％の粘度指数改良剤、及び （ｆ） ０．０５〜３重量％のジアルキルジチオ燐酸亜
鉛で、０．９５：１〜１．０４：１の範囲の亜鉛対燐重
量比を有するジアルキルジチオ燐酸亜鉛、からなり、然
も、前記潤滑油組成物の灰分含有量が１．５重量％より
少ない潤滑油組成物。9. A base oil of lubricating oil viscosity of the main component amount, (b) 1 to 10% by weight of ashless dispersant, (c) 1 to 10% by weight of overbased sulfurized alkyl phenate detergent (D) 0.05 to 2% by weight of an antioxidant, (e) 1 to 15% by weight of a viscosity index improver, and (f) 0.05 to 3% by weight of a zinc dialkyldithiophosphate. A lubricating oil composition comprising a zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio in the range of from 95: 1 to 1.04: 1, wherein said lubricating oil composition has an ash content of less than 1.5% by weight Stuff. 【請求項１０】 請求項１に記載の潤滑油組成物を用い
ることからなる、機械部品の摩耗を減少させる方法。10. A method for reducing the wear of machine parts, comprising using the lubricating oil composition according to claim 1. 【請求項１１】 次の成分： （ａ） 主成分量の潤滑油粘度の基礎油、 （ｂ） ０〜２０重量％の無灰分散剤、 （ｃ） ０〜２０重量％の過塩基性硫化アルキルフェネ
ート清浄剤、 （ｄ） ０〜１０重量％の酸化防止剤、 （ｅ） ０〜２０重量％の粘度指数改良剤、及び （ｆ） ０．０５〜５重量％のジアルキルジチオ燐酸亜
鉛で、０．９５：１〜１．０４：１の範囲の亜鉛対燐重
量比を有するジアルキルジチオ燐酸亜鉛、を一緒に混合
することからなり、然も、前記潤滑油組成物の灰分含有
量が１．５重量％より少ない潤滑油組成物の製造方法。11. The following components: (a) a base oil of lubricating oil viscosity in the main component amount; (b) 0-20% by weight of an ashless dispersant; (c) 0-20% by weight of an overbased alkyl sulfide. A phenate detergent, (d) 0-10% by weight antioxidant, (e) 0-20% by weight viscosity index improver, and (f) 0.05-5% by weight zinc dialkyldithiophosphate, A zinc dialkyldithiophosphate having a zinc to phosphorus weight ratio in the range of 0.95: 1 to 1.04: 1, wherein the lubricating oil composition has an ash content of 1. A method for producing a lubricating oil composition of less than 5% by weight. 【請求項１２】 請求項１１に記載の方法により製造し
た潤滑油組成物。12. A lubricating oil composition produced by the method according to claim 11.
JP10072383A 1997-03-20 1998-03-20 Low-ash lubricant containing ultra-neutral zinc dialkyldithiophosphate Pending JPH10265791A (en)

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US08/822,251 US5728656A (en) 1997-03-20 1997-03-20 Lower-ash lubricating oil having ultra-neutral zinc dialkyldithiophosphates

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CA2231295A1 (en) 1998-09-20
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SG71765A1 (en) 2000-04-18
CA2231295C (en) 2006-06-06

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